Composite Yarn, Manufacturing Process and Textile Surface Comprising Such a Yarn

ABSTRACT

A composite yarn comprising a continuous multifilament core yarn incorporated in a matrix, is characterized in that the matrix comprises at least one polymer material and at least one reinforcing filler, the reinforcing filler being formed from functionalized particles, said particles having a median size (d v50 ) of less than 40 μm. 
     A process for manufacturing such a composite yarn, comprises at least one step of depositing, by coating or extrusion, a matrix comprising a polymer and a reinforcing filler, onto a core yarn. 
     A textile surface comprises at least one such composite yarn.

This application is a continuation of U.S. Ser. No. 17/048,600, which isa 371 national phase entry of PCT/EP2019/060238, filed Apr. 19, 2019,which claims priority to FR 1853527 filed Apr. 20, 2018 and FR 1858616filed Sep. 21, 2018, which are herein incorporated by reference in theirentirety.

The present invention, which is disclosed below, relates to the generalfield of composite yarns, generally obtained by coating a continuousmultifilament yarn with a matrix comprising at least one polymer; oftextiles made from these yarns, and to sunblinds, or other sun-blocking,sun-screening or sun-shielding, made from such textiles or yarns.

Composite yarns are technical yarns that are well known and commonlyused, which generally comprise:

-   -   a core including a continuous multifilament yarn (i.e. a yarn        formed from several filaments) which is generally twisted;    -   a matrix, containing at least one polymer material, for example        a chlorinated polymer material such as polyvinyl chloride (PVC),        a plasticizer, and usually a flame-retardant system composed of        one or more mineral fire-retardant fillers; and    -   a sheath or envelope.

Mineral fire-retardant fillers are insoluble mineral solid substancesand are usually intended to be dispersed by a mechanical means in anorganic matrix. Fire-retardant fillers are used for improving the fireresistance of a material. Fire-retardant fillers are typically chosenfrom halogenated, organophosphorous (phosphonate, phosphinate,phosphate, etc.), boron-based or nitrogenous molecules, metal hydroxidesof the (M(OH)_(n)) type, in which M is a metal, for instance aluminum ormagnesium, or antimony oxides such as antimony trioxide or pentoxide.Many applications require flame-retardant materials (i.e., materialswith fire-resistance properties). To this end, at least onefire-retardant filler may be incorporated into the material. It is alsonecessary to adapt the formulation thus obtained to the applicationconditions. To do this, other materials may be present in the matrix,such as a viscosity reducer, which makes it possible to adjust theviscosity of the chemical preparation intended for the manufacture ofthe matrix of the composite yarn.

A composite yarn is generally obtained by depositing a polymer on thecontinuous multifilament yarn or “core yarn” (also known as the “fiber”)which usually has a torsion. Two techniques are mainly used for thispurpose: the “plastisol” technique, comprising the coating of the coreyarn with at least one layer of plastisol, said plastisol layercomprising the polymer, the plasticizer, and optionally other componentssuch as fillers, followed by gelation of the plastisol around the coreyarn; and the “extrusion-coating” technique, comprising the heating ofthe polymer from the solid form to the liquid form in an extruderfollowed by deposition on the core yarn and then calibration with a die.The term “plastisol” designates a product obtained from a dispersion ofa polymer in a plasticizer generally in the form of an oil. Thisdispersion is heated, which means that the plasticizer, starting at acertain temperature, becomes a solvent of the polymer. There is thus achange from a two-phase medium to a one-phase medium. Thistransformation, which is a sort of gelation, is irreversible. The“extrusion-coating” technique is reserved exclusively for extrudablethermoplastic polymers.

In general, the center of the composite yarn is formed from a zone inwhich all the filaments are concentrated. This zone is usually very poorin polymer. Therefore, the filaments are generally in direct contactwith each other. The lack of separation between the filaments, and theabsence of cohesion due to the lack of polymer, lead to pulling duringoperations for cutting of the textiles made with these composite yarns:if the sheath is cut, the filaments are no longer maintained in place,and can easily be pulled. This poses a problem over time since thepulled filaments create zones of fragility, which can diminish themechanical properties of the composite yarns. This is particularly truein the case of composite yarns made with textile glass yarns, since thelatter are very water-sensitive and, via a capillarity effect, the waterwhich can infiltrate into the composite yarn can after a certain timestrongly degrade the mechanical properties.

To overcome this problem, various technical solutions have beenimplemented, including the solution described in patent application WO03/056082. Said document describes a composite yarn obtained by coatingon each filament. It is thus possible to produce a flame-retardantcomposite yarn by depositing a flame-retardant coating on the compositeyarn obtained on conclusion of a first coating free of filler. However,individual coating of the filaments stiffens the composite yarn, whichmakes it difficult to manipulate the textile obtained from thiscomposite yarn, and may go as far as to render it unsuitable for use asa fabric for blinds according to the prescriptions of standard EN 13561by giving it a “memory” after rolling up, which will greatly affect itsappearance after a few cycles of use. Standard EN 13561 concernsexternal blinds, and includes requirements for performance, including inrelation to safety.

Patent application WO 2011/033130 itself describes an improvement ofpatent application WO 03/056082, in that the process for manufacturingthe composite yarn comprises a preliminary step of mechanical opening;preferably splaying of the individual filaments of which the core yarnis composed (so as to allow the accessibility of the matrix to each ofthe filaments). However, the process described in WO 2011/033130 is verycomplicated to implement. Furthermore, the core yarn must be able towithstand a substantial mechanical stress generated by the mechanicalopening of the individual filaments of which it is composed. This limitsthe choice of the core yarn.

Textiles obtained from composite yarns, generally by weaving, andintended for making blind fabrics, are subject to fire performanceregulations in various jurisdictions.

In Germany, there is a class under standard DIN 4102-1, composed ofthree categories which define the reaction to fire of materials (code B1to B3). Code B1 denotes the most stringent classification for an organicmaterial. It is generally required for solar protection textilesespecially in Germanophile regions and, by influence, in NorthernEurope.

In France, there is a class under standard NF P92-507, composed of fivecategories (or classes) which define the fire reaction of materials(code M0 to M4). This classification is based, for unmeltable materialssuch as fabrics based on inorganic fibers, on the duration ofpersistence of flames after the removal of a burner, on the destroyedlength of specimens, and also on the possible dripping of enflamed dropsduring the performance of the test under the standard NF P92-503.Standard NF P92-507 describes a class which utilizes tests carried outunder standard NF P92-503. For meltable materials, additional tests arerequired according to the standards NF P92-504 and NF P92-505.Combustibility is the heat emitted by total combustion of the material,whereas the flammability is the amount of flammable gas produced by thematerial. Code M1 denotes non-flammable combustible materials, andapplies especially to solar protection textiles intended for the Frenchmarket and also, by influence, to the markets of Southern Europe.

At the present time, the French and German classifications, althoughstill widely used, are in the process of being supplanted by theEuropean standard EN 13-501-1 which defines “euroclasses”.

Euroclasses define fire performance. They are used, inter alia, tocharacterize products for construction and for the fitting of buildings.They are more complete than each of the French and German classes takenindividually, since they take into account the fire performance of thematerial denoted A1, A2, B, C, D or F according to the level of energyreleased, the opacity of the fumes released (amount and speed) denoted“s” for “smoke” (code s1 to s3) and also any projected enflamed dropletsand debris denoted “d” for “droplets” (code d0 to d2). The commoncommercial composite yarns obtained by coating a mineral core yarn suchas textile glass yarn (or glass fiber) with a plastisol, which is evenhighly flame-retardant, make it possible to prepare textiles which atbest meet the fire performance criteria of euroclass Cs3d0 of thestandard EN 13-501-1. Ideally, they should meet the fire performancecriteria of euroclass Bs2d0 of the standard EN 13-501-1. However, at thepresent time, no commercial composite yarn obtained by coating a flameretardant PVC plastisol on a mineral core yarn such as glass textileyarn makes it possible to prepare solar protection textiles which meetthe fire performance criteria of euroclass Bs2d0 or Bs3d0 of thestandard EN 13-501-1.

To prepare flame-retardant composite yarns, use is usually made offire-retardant fillers dispersed in the polymer of the matrix. Thesefire-retardant fillers are of very diverse size and form.

Patent EP 0900294 describes a composite yarn such that the polymermaterial which constitutes its matrix is chlorinated, and comprising afire-retardant filler of ternary composition combining an oxygenatedantimony compound (in general antimony trioxide), a hydrated metal oxideand a zinc borate, the total composition of inorganic material of thecomposite yarn being between 4 and 65%. The plasticizer generallycomprises at least one organic phthalate and is free of phosphate.However, certain phthalates are reputed to be toxic and antimony saltsare suspected of having toxicity.

Patent application WO 2010/001240 describes an improvement of patent EP0900294, in that the flame-retardant plastisol comprises a lead-freechlorinated polymer, in that the plasticizer is free of orthophthalateand in that the fire-retardant filler is free of antimony and comprisesmetal hydrate and a zinc salt. However, the content of flame-retardantagent is high, whereas the content of plasticizer is relatively low tocomply with the fire classes, which leads to stiffness of the compositeyarn and thus to difficulties for obtaining, from such a composite yarn,blind fabrics that are also in accordance with the performancerequirements prescribed by standard EN 13561.

There is thus a need for composite yarns which have improved fireperformance relative to the prior art, which are simple to manufactureand which allow the production of blind fabrics which meet therequirements of standard EN 13561.

One aspect of the present disclosure is to present improvements in thefire performance of composite yarns. Another aspect of the presentdisclosure is to provide a process for manufacturing composite yarnsthat is simple to perform. Another aspect of the present disclosure isto allow the use of glass textile yarn, as core yarn, with low torsionand containing a standard sizing for the purpose, among other things, ofreducing the composite yarn manufacturing costs. Another aspect of thepresent disclosure is to provide a process which complies with theenvironmental standards and which, in particular, uses components thatare not suspected of being toxic and which limits the emission ofvolatile organic compounds (VOCs).

Thus, according to a first aspect, a composite yarn comprising acontinuous multifilament core yarn incorporated in a matrix, ischaracterized in that the matrix comprises at least one polymer materialand at least one reinforcing filler, the reinforcing filler being madeof functionalized particles, said particles having a median size(d_(v50)) of less than 40 μm.

Advantageously, the composite yarn has a titer (or count) which is lessthan the titer of the composite yarns of the prior art. Thus, typically,the composite yarn, when the core yarn has a titer of 68 tex, has atiter of 135-140 tex whereas the composite yarns of the prior art have atiter of about 165 tex for the same core yarn. This advantageously makesit possible to reduce the mass per unit area and the thickness oftextiles made from composite yarns by, respectively, about 10 to 20%,and about 10 to 15%.

The continuous multifilament core yarn has preferably a torsion withinthe range of from 20 to 40 rounds per meter.

According to a preferred embodiment, the torsion of the core yarn isbetween 28 and 40 turns per meter.

According to an even more preferred embodiment, the torsion of the coreyarn is 28 turns per meter.

Preferably, the functionalized particles of the reinforcing filler (orreinforcing particles) are dispersed throughout the matrix of thecomposite yarn, the matrix being in contact with the core yarnfilaments.

Particularly preferably, some of the reinforcing filler is present inthe inter-filament interstices of the core yarn. Advantageously, thesmallest particles of the reinforcing filler are present in theinter-filament spaces interstices of the core yarn.

In any case the matrix forms generally a continuous medium in which thefunctionalized particles are dispersed.

Preferably, the dispersion of the functionalized particles in the matrixis homogeneous. By “homogeneous”, it should be understood that theconcentration in functionalized particles in the matrix is of the sameorder of magnitude at any point of said matrix.

According to a preferred embodiment disclosed herein, the composite yarnis made of the core yarn, the matrix, and a sheath.

The term “between X and Y”, X and Y being any numerical values, meansbetween X and Y, limits excluded. The term “within the range from Z toT”, Z and T being any numerical values, means between Z and T, limitsincluded.

The term “A and/or B”, A and B being any characteristics, means “A” or“B” or “A and B”.

The term “tex” means, as is usual for a person of ordinary skill in theart, the mass in grams of one kilometer of yarn.

The term “matrix” means an element comprising at least one polymermaterial in contact with the core yarn.

Preferably, the particles have a hardness (Mohs) less than or equal tothe hardness of the material constituting the core yarn.

Mohs hardness is a measurement of the hardness of minerals. Mohs scaleis based on ten readily available minerals. The hardness scale rangesfrom 1 (for talc) to 10 (for diamond). It is measurable by comparison(capacity of one to scratch the other) of a mineral with two otherminerals whose hardness is already known. In general, this value isgiven by the product suppliers. Thus, the hardness of textile glass yarnformed from multifilaments is 5.5. Textile glass yarn is commonly calledsilionne. Textile glass yarn is a twisted assembly of various filamentsof sized silionne. The term “sized” will be explained herein below.According to a preferred embodiment, the Mohs hardness of the particlesconstituting the reinforcing filler is at least 1 and not more than 5.5,including for example increments of 0.5 between these values. In otherwords, this hardness is in the range from 1 to 5.5.

If the hardness of the reinforcing particles is less than 1, thereinforcing filler is generally friable and therefore it becomesdestructured because it cannot withstand the shear during themanufacturing steps of the composite yarn. If the hardness of thereinforcing particles is greater than 5.5, the reinforcing filler maylocally damage the filaments constituting the core yarn.

The term “size” (or “average size”) means, as is usual, the diameterwhich would be had by the theoretical sphere behaving in the same manneras a particle under consideration during the chosen particle sizeanalysis operation. The term “diameter” or “equivalent diameter” is alsoused.

In the technical field under consideration, the measurements aregenerally taken by screening with a succession of vibrating screens orby laser particle size analysis (using a diffraction laser). Theparticle size is preferably measured by laser particle size analysis. Amachine that may be used for laser particle size measurement istypically a Malvern Instruments brand machine, for example a MalvernMasterizer 2000 Instrument machine. This machine makes it possible,inter alia, to determine the volume distribution of the particles, andin particular the dimensions d_(v50), d_(v10) and d_(v90) explainedhereinbelow. It is usual to combine, as is known to those of ordinaryskill in the art, the use of a powder drier, for example of Scirocco2000 type, which makes it possible to dry the dry powder which feeds thelaser particle size analyzer.

The median size (d_(v50)), or size (d_(v50)) gives the median size: 50%(by volume) of the particles have a smaller size, and 50% (by volume) ofthe particles have a larger size. The particles have a median size(d_(v50)) of less than 40 μm, and preferably less than 30 μm, andgenerally greater than 5 μm, and preferably greater than 15 μm.Preferably, the median size (d_(v50)) is between 5 μm and 40 μm, andstill more preferably between 15 μm and 30 μm, or within the range from15 μm to 30 μm, including for example increments of 1 μm therebetween.

If the median size of the reinforcing particles (d_(v50)) is less than 5μm, too large an amount of particles of the reinforcing filler ispresent in the inter-filament interstices of the core yarn. In processterms, this generally results in the surface area of these particlesbeing too great and leads to an increase in the viscosity of the polymermaterial constituting the matrix when it is deposited. If the mediansize (d_(v50)) of these reinforcing particles is greater than 40 μm, toofew of these reinforcing particles are present in the inter-filamentinterstices of the core yarn. In process terms, this generally resultsin the dispersion of the particles of the reinforcing filler in theinter-filament interstices of the core yarn being difficult andtherefore insufficient. The breaking strength of the composite yarn isthen generally judged insufficient.

The size (d_(v10)) gives the size below which 10% (by volume) of theparticles have a smaller size, and 90% (by volume) of the particles havea larger size. The particles generally have a size (d_(v10)) of lessthan 15 μm, and preferably within the range from 1 μm to 15 μm.

If the size (d_(v10)) of the reinforcing particles is less than 1 μm,too large an amount of particles of the reinforcing filler is present inthe inter-filament interstices of the core yarn. In process terms, thisgenerally results in the surface area of these particles being too greatand leads to an increase in the viscosity of the polymer materialconstituting the matrix when it is deposited. If the size (d_(v10)) ofthe reinforcing particles is greater than 15 μm, too few of thesereinforcing particles are present in the inter-filament interstices ofthe core yarn. In process terms, this generally results in thedispersion of the particles of the reinforcing filler in theinter-filament interstices of the core yarn being difficult andtherefore insufficient. The breaking strength of the composite yarn isthen generally judged insufficient. The size (d_(v90)) gives the sizebelow which 90% (by volume) of the particles have a smaller size, and10% (by volume) of the particles have a larger size. The particlesgenerally have a size (d_(v90)) of less than 90 μm, preferably withinthe range from 30 μm to 90 μm, and still more preferably from 30 μm to80 μm. If the size (d_(v90)) of the reinforcing particles is less than30 μm, too large an amount of particles of the reinforcing filler ispresent within the inter-filament spaces of the core yarn. In processterms, this generally results in the surface area of these particlesbeing too great and leads to an increase in the viscosity of the polymermaterial constituting the matrix when it is deposited. If the size(d_(v10)) of the reinforcing particles is greater than 90 μm, too few ofthese reinforcing particles are present in the inter-filamentinterstices of the core yarn. In process terms, this generally resultsin the dispersion of the particles of the reinforcing filler in theinter-filament interstices of the core yarn being difficult andtherefore insufficient. The breaking strength of the composite yarn isthen generally judged insufficient. In the textile field using thecomposite yarn, the nominal value of the average diameter of each of thefilaments of the core yarn is generally within the range from 3.5 μm to13 μm, typically in the range from 3.5 μm to 9 μm, still more preferablyin the range from 6 μm to 9 μm, for example 6 μm or 9 μm. This nominalvalue is generally given by the core yarn supplier. Other nominal valuesmay be envisaged for other uses of the composite yarn.

According to a preferred embodiment, the ratio between the median size(d_(v50)) of the reinforcing particles and the diameter of each of thefilaments of the core yarn is generally in the range from 0.15:1 to12:1, preferably from 1.5:1 to 5:1.

According to a preferred embodiment, the weight percentage ofreinforcing filler present in the composite yarn is within the range of0.5 to 30%. According to a more preferred embodiment, the weightpercentage of reinforcing filler present in the composite yarn is withinthe range of 0.5 to 20%. According to an even more preferred embodiment,the weight percentage of reinforcing filler in the composite yarn iswithin the range of 1 to 10%.

According to a preferred embodiment, the reinforcing filler is chosenfrom the group formed by functionalized fillers, preferably from thegroup formed by functionalized glass beads, functionalized calciumcarbonate, and functionalized talc.

The functionalized glass beads have a hardness of 5.5. Thefunctionalized calcium carbonate has a hardness of 3.0. Thefunctionalized talc has a hardness of 1.0.

The term “functionalized” means “surface-treated”, i.e., a functionalityhas been added to the surface of the particle via at least one organicgroup. This functionalization is performed with at least one compound,known as a functionalizing agent. The functionalization makes itpossible to create a “chemical bridge” between the filler and itsenvironment, which in this case is the matrix. It is thus possible tochemically link (for example via covalent bonds) or physicochemicallylink (for example via hydrogen bonds) the filler, the core yarn, and thematrix. Advantageously, this makes it possible to obtain a substantiallyhomogeneous medium in which all the constituents are bound together viachemical bonds of organic type. Advantageously, this gives the materialsubstantial cohesion and homogeneity of the mechanical properties. Thisis coherent with the use of the term “reinforcing filler”. In otherwords, the reinforcing filler is fully attached to the polymerconstituting the matrix and also to the core yarn.

Moreover, the reinforcing filler has a particle size that is smallenough for some of them to be present in the inter-filament intersticesof the core yarn, which advantageously allow fillings of theinter-filament interstices, preferably of all of the inter-filamentinterstices.

As regards talc, which is composed of phyllosilicate particles, thefunctionalizing agent is generally chosen from the group formed byoxysilanes (or siloxanes) and oxygermanes bearing at least one organicgroup. This is described, for example, in WO 2014/207397.

The functionalized glass beads are generally made by chemical grafting,covalently and directly or indirectly, of a reagent onto the surface ofthe glass. This is described, for example, in WO 2014/083162.Functionalized glass beads are marketed by the company Sovitec under thename Microperl® or Omicron®.

Calcium carbonate is generally functionalized by chemical grafting ofreagents onto the surface. The processes performed are similar to thoseused for glass beads.

Preferably, the reinforcing filler is functionalized with at least onecompound chosen from silanized agents such as silanes, for example alkylalkoxy silanes; epoxies, among which mention may be made of epoxysilanesand DGEBA (Bisphenol A diglycidyl ether); and polyisocyanates such asMDI derivatives (or 4,4′-MDI for 4,4′-diphenylmethane diisocyanate) orHDI (for hexamethylene diisocyanate).

Preferably, the reinforcing filler is functionalized with at least onecompound chosen from silanized agents, epoxies, and polyisocyanates, andeven more preferably silanized agents.

Silanized agents are compounds comprising at least one silyl group, suchas alkyl alkoxysilanes, alkylsilyl halides, for example such astrimethylsilyl chloride or diemethylsilyl dichloride, tetramethylsilane,tetraethoxysilane, dimethylsiloxane, 1,1,1,3,3,3-hexamethyldisilazane,etc.

By “silyl”, is meant a radical derived from silane.

By “alkyl”, is meant a radical derived from alkane, comprising from 1 to20 carbon atoms, preferably from 1 to 10 carbon atoms, and morepreferably from 1 to 5, carbon atoms.

By “alcoxysilane”, is meant a compound comprising a divalent group —Si—Oand an alkyl group comprising from 1 to 20, preferably from 1 to 10, andmore preferably from 1 to 5, carbon atoms.

Silanes are preferentially used, since there is a wide range of theseproducts. Silane is the molecule of formula SiH₄. By extension, the term“silane” here and as is usual refers to any compound whose central atomis silicon such as SiHCl₃ (trichlorosilane) or tetramethylsilaneSi(CH₃)₄ or tetraethoxysilane Si(OC₂H₅)₄. The functionalized reinforcingfiller is referred to as a silanate if it is functionalized with asilane, that is, a covalent bond is created between at least one silylgroup of the silane and a particle of the reinforcing filler. Forexample, silanization by means of trimethylsilyl chloride createstrimethylsilyl groups covalently bonded to the particles, orsilanization by means of dimethylsilyl dichloride creates dimethylsilylgroups covalently bonded to the particles. A person of ordinary skill inthe art can readily identify a grade that is perfectly suited to thesituation, as a function of the filler, of the core yarn and of thematrix. Epoxies and polyisocyanates are preferred most particularly inthe case where the core yarns are of organic origin (polyesters,polyamides, polyvinyl alcohol, etc.).

According to a preferred embodiment, the matrix further comprises atleast one fire-retardant filler.

Fire-retardant fillers are well known to those of ordinary skill in theart. They are generally chosen from oxygenated antimony compounds, forexample antimony trioxide, certain zinc salts, including zinchydroxystannate or zinc borate, hydrated metal oxides, the metal ofwhich is chosen from the group formed by aluminum, magnesium, tin andzinc, for example an alumina hydrate such as alumina trihydrate or amagnesium hydrate such as magnesium hydroxide, and phosphorus-basedceramics which act as intumescent systems.

The constituent material of the core yarn is preferably chosen fromsilionne, basalt, aramids, polyesters, polyamides, carbon, and polyvinylalcohol. In a particularly preferred manner, the constituent material ofthe core yarn is silionne. As indicated above, silionne has a Mohshardness of 5.5.

In the case where the constituent material of the core yarn is silionne,it is known that the core yarn may be formed from a “standard” textileglass yarn or from a “specific” glass yarn.

Standard textile glass yarn has a torsion generally within the rangefrom 20 to 40 turns per meter. The torsion is typically 28 turns permeter for a core yarn tex of 33 tex or 68 tex, or 40 turns per meter fora core yarn of 22 tex. Standard textile glass yarn further comprises asizing generally based on starch, the purpose of which is to protect thesilionne filaments and to ensure their cohesion. This is then referredto as a sized textile glass yarn. The compositions of such sizing are ingeneral developed by the companies which commercialize these core yarns,which do not disclose them.

The sizing is deposited on the individual filaments composing thetextile glass yarn during what is called in this industry the “forming”operation which consists in spinning the filaments of molten glassthrough the holes of a die at high speed. This sizing is generallydeposited on the surface of the filaments in the form of an aqueousemulsion during the manufacture of the core yarn. It generallyrepresents from 0.5% to 1.5% of the weight composition of the core yarn.For textile yarns, the role of the sizing is to protect the filaments toallow their manipulation and to reduce the phenomenon of staticelectricity during weaving. The textile sizing is usually composed of anadhesive agent (which is generally starch), and possibly at least onewetting agent (intended to improve the impregnation of the yarn) and/orat least one lubricant. In contrast with the specific textile glassyarn, the standard textile glass yarn does not include any couplingagent in its sizing.

Thus, the standard textile glass yarn is generally a textile glass yarnhaving a torsion in the range from 20 to 40 turns per meter, andcomprising a sizing comprising, preferably being formed from, at leastone adhesive agent, and possibly at least one wetting agent and/or atleast one lubricant.

The specific textile glass yarn, usually used in the applications forcoating textile glass yarn with a PVC plastisol, has a torsion generallyin the range from 40 to 80 turns per meter and/or what is referred to asspecific sizing, which, in addition to the sizing of the standardtextile glass yarn, contains at least one adhesion promoter and/or atleast one coupling agent for the sizing. The torsion value is generallylinked to the final application concerned. The adhesion promoter and/orthe coupling agent is/are intended to allow adhesion (mainly by creatingat least one chemical bond) between the constituent filaments of thetextile glass yarn and the adhesion promoter(s) and/or coupling agent(s)and, furthermore, between the adhesion promoter(s) and/or couplingagent(s) and the polymer(s) constituting the matrix. The constituentfilaments of the textile glass yarn and the polymer(s) are thuschemically bonded. Preferably, the specific sizing further comprises atleast one organic binder and/or at least one lubricant. The adhesionpromoters/coupling agents are generally silanes. Each textile glass yarnmanufacturer has his own sizings, the exact chemical compositions ofwhich are known only to him. There are thus sizings that are speciallydeveloped for promoting silionne/PVC adhesion such as the sizings TD52and TD53 from the company VETROTEX and sizings specially developed forpromoting adhesion of silionne with various types of polymers such asthe sizings TD22 and TD37 from the company VETROTEX.

Thus, the specific textile glass yarn is generally a textile glass yarnwith a torsion in the range from 40 to 80 turns per meter, and/orcomprising a sizing comprising, preferably formed from, at least oneadhesive agent, and at least one adhesion promoter and/or at least onecoupling agent.

The specific textile glass yarn is thus much more expensive than thestandard textile glass yarn.

In a particularly advantageous manner, the composite yarn may comprise acore yarn which is a standard textile glass yarn, rather thanmandatorily a specific textile glass yarn.

Without wishing to be limited by any theory, the Applicant thinks thatthis advantage is obtained by means of a certain amount of control ofthe bonding between the polymer constituting the matrix and the coreyarn, and by virtue of the presence in the matrix of the functionalizedparticles which play an intermediate role and which behave like“articulations” between the constituent filaments of the textile glassyarn and the constituent polymer of the matrix. These functionalizedparticles create chemical bonds between the standard sizing of the coreyarn and the polymer constituting the matrix, which is not possibleaccording to the prior art.

In the case of textile applications, this thus advantageously makes itpossible to replace the specific textile glass yarn with a standardtextile glass yarn, which allows an appreciable reduction in the cost ofmanufacture of the composite yarn, of the order of 25%, and which opensthe panel of potential suppliers of core yarns for the composite yarnmanufacturer, especially towards those which have the largest worldwideproduction capacities, for example the Asiatic suppliers manufacturingtextile glass yarns intended for producing printed circuit boards.Specifically, not only is the raw material of the core yarn lessexpensive, in particular by avoiding the use of special and expensiveorganic products for the sizing (namely at least one adhesion promoterand/or at least one coupling agent), but also it is possible, by meansof less twisting of the core yarns which are textile glass yarns, tolimit the time of passage of these yarns on the twisting machinesgenerally used in textile production.

As will be shown in the examples, the qualities of the composite yarnobtained by using a core yarn which is a standard textile glass yarn arenot compromised, or are even superior to those of the composite yarns ofthe prior art using a core yarn which is a specific textile glass yarn.Without wishing to be limited by any theory, the Applicant thinks thatit is by virtue of easier access to the inter-filament interstices,permitted by the functionalized particles present in the matrix.

The core yarn of the composite yarn may thus be a standard textile glassyarn.

The core yarn of the composite yarn may also be a specific textile glassyarn.

The softening point or melting point of the constituent material of thecore yarn must be higher than the temperature of implementation of thepolymer material of the matrix of the composite yarn. For example, thesoftening point of the constituent material of the core yarn when it isa textile glass yarn is at least 20° C. higher, preferably at least 30°C. higher and even more preferably at least 50° C. higher than thetemperature of implementation of the polymer material of the matrix ofthe composite yarn. By way of example, the temperature of implementationof the polymer material of the matrix of the composite yarn is typicallyin a range from 50 to 180° C. The softening point of the constituentmaterial of the core yarn, when said yarn is a textile glass yarn, istypically about 600° C.

According to a preferred embodiment, the composite yarn furthercomprises at least one layer, also termed “sheath” or “envelope”enveloping said matrix, the layer comprising at least one polymermaterial and at least one reinforcing filler. This layer is usuallydeposited in the same manner as the matrix, preferably by coating.According to a preferred embodiment, the composite yarn is formed fromthe core yarn, the matrix and the sheath.

Preferably, the polymer material of this layer is of the same chemicalnature as the polymer material of the matrix. The term “same chemicalnature” means of compatible chemical composition, as is known to thoseof ordinary skill in the art. According to a preferred embodiment, thereinforcing filler of said layer is of the same chemical nature as thereinforcing filler of said matrix. Advantageously, this identity ofchemical nature makes it possible to obtain a composite yarn which hasbetter homogeneity, i.e., the core yarn, the matrix, and the layer ofwhich it is composed interact in terms of sorption and adhesion.

In addition, at least one other additive may be incorporated anddistributed in the matrix, in the layer or both (layer and matrix), suchas one or more fire-retardant fillers, a pigmentary filler and/or a heatstabilizer and/or a UV stabilizer.

Preferably, the sheath further comprises at least one fire-retardantfiller. Such a fire-retardant filler is chosen from the fire-retardantfillers known to those of ordinary skill in the art and described above.

The disclosure advantageously makes it possible to limit the amount (byweight) of fire-retardant filler present in the composite yarn Thus,usually, the amount (by weight) of fire-retardant filler in thecomposite yarn is generally more than 1.5% and less than 7.5%, e.g.,about 3% by weight relative to the total weight of the composite yarn,to obtain a level of flame retardancy similar to that of the compositeyarns of the state of the art, for which the amount by weight of flameretardant filler is most often from 8 to 12% by weight relative to thetotal weight of the composite yarn.

The disclosure advantageously makes it possible to obtain a compositeyarn which, for an identical amount (by weight) of fire-retardantfiller, has fire resistance performance that is particularly improvedrelative to that of the composite yarns of the prior art. Thus, it ispermitted, for the first time, to manufacture a composite yarn whosecore yarn is formed from silionne, which meets the criteria Bs2d0 orBs3d0 of Euroclasse standard EN 13501-1. Without wishing to be bound byany theory, the Applicant thinks that the inorganic nature of thereinforcing filler allows local dispersion of the heat supplied by thefire. In addition, filling of the inter-filament interstices with thereinforcing particles makes it possible to eliminate a “chimney” effectassociated with the existence of a lack of material at the center of thecore yarn, which favors flame propagation.

According to one embodiment, the composite yarn comprises a continuousmulti-filament core yarn and a matrix, the matrix comprising:

-   -   (i) at least one polymer material, the polymer being chosen from        the group consisting of PVCs, polyacrylates, polyolefins,        polyesters, polyvinyls, polystyrenes, polyurethanes, EVA        polymers and polyamides, and    -   (ii) at least one reinforcing filler, the reinforcing filler        being constituted by particles dispersed in the polymer material        of the matrix and present in the inter-filament interstices of        the core yarn, said particles being functionalized and having a        median size (d_(v50)) less than 40 μm,

the composite yarn further comprising a flame-retardant filler in anamount of approximately 0.5 to 5% by weight and being such that thetextile surfaces obtained from said yarn meet the performancerequirements prescribed by the standard EN 13561 (more than 10 000cycles).

By “textile surface”, is meant a mechanical assembly of yarns, such as afabric, a non-woven, a knit, a textile grid, etc. By “textile surfaceobtained from said yarn”, is meant that the yarn assembly is thecomposite yarn.

According to one embodiment, the composite yarn comprises a continuousmulti-filament core yarn and a matrix, the matrix comprising:

-   -   (i) at least one polymer material, the polymer being chosen from        the group consisting of PVCs, polyacrylates, polyolefins,        polyesters, polyvinyls, polystyrenes, polyurethanes, EVA        polymers and polyamides, and    -   (ii) at least one reinforcing filler, the reinforcing filler        being constituted by particles dispersed in the polymer material        of the matrix and present in the inter-filament interstices of        the core yarn, said particles being functionalized and having a        median size (d_(v50)) less than 40 μm,

the composite yarn further comprising a flame-retardant filler in anamount of approximately 0.5 to 5% by weight, and being such that thetextile surfaces obtained from said yarn meet the fire performancerequirements of class M1 of the standard NF P-92-507.

According to one embodiment, the composite yarn comprises a continuousmulti-filament core yarn and a matrix, the matrix comprising:

-   -   (iii) at least one polymer material, the polymer being chosen        from the group consisting of PVCs, polyacrylates, polyolefins,        polyesters, polyvinyls, polystyrenes, polyurethanes, EVA        polymers and polyamides, and    -   (iv) at least one reinforcing filler, the reinforcing filler        being constituted by particles dispersed in the polymer material        of the matrix and present in the inter-filament interstices of        the core yarn, said particles being functionalized and having a        median size (d_(v50)) less than 40 μm,

the composite yarn further comprising a flame-retardant filler in anamount of approximately 5 to 15% by weight, and being such that thetextile surfaces obtained from said yarn meet the fire performancerequirements of Euroclass Bs2d0 or Bs3d0 of the standard NF P13501-1.

According to a second aspect, the present disclosure also covers aprocess for manufacturing a composite yarn according to the firstaspect, said process comprising at least one step of depositing, bycoating or extrusion, a matrix comprising at least one polymer materialand at least one reinforcing filler, onto a core yarn.

The matrix incorporates, in addition to the polymer material, at leastone reinforcing filler and possibly at least one other additive such asa flame-retardant filler.

The polymer used for the deposition is a conventional polymer such as aPVC, a polyacrylate, a polyolefin, a polyester, a polyvinyl, apolystyrene, a polyurethane, an ethylene-vinyl acetate (or EVA) polymeror a polyamide. PVCs and polyacrylates are generally used by thedeposition by coating, typically with plastisol technology. Polyolefins,polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers andpolyamides are generally used by extrusion deposition.

Preferably, the reinforcing filler is dispersed throughout the polymerbefore deposition. In other words, the reinforcing filler is mixed withthe polymer, in particular when the latter is heated for the depositionif the polymer is deposited in liquid form. It may be mixed as a mixtureof powders when the polymer is in powder form. It may also be intimatelymixed with the polymer by an extrusion operation (“compounding”) whenthe polymer is in the form of granules.

Such deposition is carried out particularly preferably such that aproportion of the filler is disposed in the inter-filament intersticesof the core yarn. This is generally carried out by adjusting therheological characteristics of the matrix during deposition, as is knownto the person of ordinary skill in the art.

Preferably, the depositing step is performed by coating with a plastisolon the filaments of the core yarn, the plastisol more preferably beingbased on polyvinyl chloride (PVC) or alternatively based on acrylicresin (polyacrylate). By “based on” is meant according to the invention“mainly comprising”.

Plastisols are well known to the person of ordinary skill in the art.They are generally pastes at room temperature obtained by dispersing apowdery synthetic resin (which is the polymer) in a liquid plasticizer.Various plastisols are described, for example, in patent application WO2010/001240.

According to a preferred embodiment, the manufacturing process furthercomprises at least one step of coating, onto the composite yarnmanufactured at the depositing step, at least one layer of polymermaterial in which is dispersed at least one reinforcing filler. In thiscase, preferably, the layer further comprises at least onefire-retardant filler.

This coating step is typically performed by coating with a plastisolonto the composite yarn obtained at the depositing step or by extrusionof a compound onto the composite yarn obtained at the depositing step,preferably by coating with a plastisol onto the composite yarn obtainedat the depositing step.

The layer incorporates at least one reinforcing filler, and possibly atleast one other additive such as a fire-retardant filler.

The polymer used for the coating is generally similar to the polymerused for the deposition. The polymer used for the coating is generallychosen from the group consisting of PVCs, polyacrylates, polyolefins,polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers andpolyamides.

The parameters of this coating step are generally similar to theparameters of the depositing step explained above, including addition bymixing one or more additives into the polymer before the coating.

Coating with a plastisol on the composite yarn obtained at thedepositing step has been explained above.

The term “compound” means a compound (which is generally granular) of aplasticized polymer (PVC, polyacrylate, etc.), or a compound (which isgenerally granular) of a polymer (polyolefin, polyester, polyvinyl,polystyrene, polyurethane, EVA, polyamide, etc.) of low glass transitiontemperature, said compound also optionally comprising at least oneadditive such as a stabilizer and/or a fire-retardant filler. The term“compound” is well known to those of ordinary skill in the art. The term“plasticized polymer” means, as it is understood to those of ordinaryskill in the art, that there is intimate mixing between the polymer anda plasticizer which has been used to plasticize it.

Preferably, in the case where the coating step is performed by extrusionof a compound, the coating step is performed by extrusion-coating of acomposite yarn obtained in the depositing step with a compound in whichis dispersed at least one reinforcing filler. The reinforcing filler hasbeen described above.

The disclosure also relates, in a third aspect, to a textile surfacecomprising at least one composite yarn according to the first aspect ormanufactured according to the second aspect.

Preferably, said textile surface is prepared by weaving.

The present disclosure will be understood more clearly in the light ofthe example that follows, which illustrates a selected embodiment of theclaimed invention without, however, limiting the scope thereof.

EXAMPLES Example 1

Two composite yarns according to one embodiment were manufactured, fromPVC plastisol, by coating a non-flame-retardant matrix comprisingsilanized glass microbeads as reinforcing filler, followed by coatingwith a flame-retardant layer itself also containing silanized glassmicrobeads as reinforcing filler on a core yarn. The core yarn wascomposed of a textile glass yarn from two different sources. Thesilanized glass beads had a hardness of 5.5 Mohs. They were sphericaland had an average diameter of 20 μm, with a d_(v50) of 30 μm, a d_(v10)of 15 μm and a d_(v90) of 80 μm, as measured for example by laserparticle size measurement using a Malvern Masterizer 2000 Instrumentmachine.

A control composite yarn was also made on the basis of the teaching ofpatent EP 0900294, with two successive coatings of the same PVCplastisol on the same core yarn.

1. Composite Yarns According to One Embodiment of the Invention

Core Yarns: Textile Glass Yarns

The textile glass yarns are characterized by the chemical composition ofthe silionne, their titer expressed in tex, the diameter and the numberof filaments of which the yarn is composed, their torsion and the typeof sizing used:

Since the sizing is the protective coating deposited immediately afterspinning the silionne, the final use of the textile glass yarnconditions the chemical nature of the sizing.

Two types of core yarn were used, respectively, for the two compositeyarns according to the embodiment:

-   -   A specific textile glass yarn specially developed for the “PVC        coating” application (and thus more expensive) bearing a        specific sizing compatible with PVC coating (silane based sizing        TD52M sold by the company Vetrotex, of unknown proprietary        composition) and also a high torsion (52 turns per meter, i.e.        “1.3Z”); it was also used for the control composite yarn;    -   a standard textile glass yarn (torsion 28 turns per meter, i.e.        “0.7Z”) covered with a starch-based sizing.

PVC Plastisols According to One Embodiment

In each case, the core yarn was coated using a first non-flame-retardantcoating containing silanized glass microbeads and then a secondsparingly flame-retardant coating also containing silanized glassmicrobeads. The compositions of the two plastisols used are given inTables 1 and 2 below.

Plastisol 1 (Matrix)

TABLE 1 Plastisol composition Component in PHR (per % weight functionComponent hundred resin) composition Plasticizer Benzoate/dioctyl 56.531.4% terephthalate Heat Liquid stabilizer of Ba/Zn 5.9 3.3% stabilizertype Inorganic Silanized glass beads 17.6 9.8% filler (Microperl ®050-20 from the company Sovitec) PVC resin PB1302 from the 100.0 55.6%company Kem-one (emulsion polymerized PVC resin of K-Wert* 67) Total180.0 100.0% *Fikentscher constant, representing the molecular mass ofthe polymer

The RV-type Brookfield viscosity of this plastisol was: 1200 mPa·s(measured with a No. 3 spindle at 23° C.).

The temperature of the yarn exiting the coating line was: 125° C.

Plastisol 2 (Layer)

TABLE 2 Plastisol composition Component in PHR (per % weight functionComponent hundred resin) composition Plasticizer Benzoate/dioctylterephthalate 45.0 23.1% Heat stabilizer Liquid stabilizer of Ba/Zn type5.0 2.6% PVC resin 1 EXT from the company Vinnolit 20.0 10.3%(suspension polymerized PVC resin of K-Wert 66) Flame- Zinchydroxystannate (Flamtard 10.0 5.1% retardant 1 H from the companyWilliam Blythe) Flame- Ceramic (Adrafoc CR-B from 5.0 2.6% retardant 2the company Adrafoc) Flame- Alumina trihydrate (Sh 30 from 5.0 2.6%retardant 3 the company Alteo) Opacifier Sachtolit L zinc sulfide fromthe 10.0 5.1% company Sachleben Inorganic filler Silanized glass beads15.0 7.7% (Microperl ® 050-20 from the company Sovitec) PVC resin 2PB1302 from the company 80.0 41.0% Kem-one (emulsion PVC resin of K-Wert67) Total 195.0 100.0%

The RV-type Brookfield viscosity of this plastisol was: 1350 mPa·s(measured with a No. 3 spindle at 23° C.).

The temperature of the yarn at the outlet of the coating line was: 135°C.

Plastisols 1 and 2 contain no viscosity reducer. This absence ofviscosity reducer is one advantage, which is very beneficial for theconservation of the plastisol and participates in reducing the emissionof VOCs during the production of the composite yarn.

Two composite yarns were thus obtained according to one embodiment, thecharacteristics of which are given in Table 3 below.

TABLE 3 Type of base yarn ECG 75 0.7Z ECG 75 1.3Z Torsion Z28 Z52 SizingStarch standard Specific (B12) (TD52M) Titer of the yarn after the1^(st) 108 tex 110 tex coating Titer of the yarn after the 2^(nd) 135tex 140 tex coating Breaking strength of the coated 50N 54N yarn(measured using a tensile testing machine with jaws specific for theyarn, at a tensile speed of 50 mm/min)

2. Control Yarn

A control yarn, of reference 165 tex, was made according to therecommendations of patent EP 0900294, starting with the core yarn whichis a specific textile glass yarn, specially developed for the PVCcoating of specific sizing type TD52M sold by the company Vetrotex andof high torsion (52 turns per meter) similar to that used for one of thetwo composite yarns according to the embodiment. Only two successivecoatings were performed with the same plastisol. The composition of theplastisol used is given in Table 4 below.

TABLE 4 Plastisol composition in % weight Component PHR (per % compo-function Component hundred resin) sition Plasticizer Diisodecylphthalate 45.43 24.2% (DIDP) Heat stabilizer Liquid stabilizer of 4.962.6% Ba/Zn type PVC resin EXT from the company 20 10.6% VinnolitFlame-retardant 1 Antimony trioxide (Triox 7.65 4.1% from the companyPLC) Flame-retardant 2 Zinc borate 7.64 4.1% Flame-retardant 3 Aluminahydrate 7.65 4.1% Opacifier Zinc sulfide (ZnS) in a 3.10 1.7%plasticizer of DIDP terephthalate type in a 70/30 ratio (weight/weight)PVC resin PB1302 from the 80 42.7% company Kem-one Lubricant Wacker ® AK50 silicone 0.93 0.5% oil from the company Wacker Chemie Diluent(viscosity C₁₁-C₁₃ isoparaffinic 10.08 5.4% reducer) fraction Isopar ® Lfrom the company Exxon Total 187.44 100.0%

The RV-type Brookfield viscosity of this plastisol was: 1300 mPa·s(measured with a No. 3 spindle at 23° C.). This value was obtained withthe addition of 5.4% of a volatile viscosity reducer, the presence ofwhich generated VOCs during the transformation of the plastisol.

The temperature of the yarn at the outlet of the coating line was: 135°C.

3. Results

The three composite yarns and the corresponding textiles obtained by thesame operation for the weaving of these composite yarns had thecharacteristics given, respectively, in Tables 5 and 6 below.

TABLE 5 Composite yarn A Composite yarn Control according to the Baccording to composite embodiment the embodiment yarn C Titer of thecore yarn 68 tex 68 tex 68 tex Diameter of each of the 9 μm 9 μm 9 μmfilaments Reference of the core ECG 75 0.7Z ECG 75 1.3Z ECG 75 1.3Z yarnTorsion of the core yarn Z28 Z52 Z52 Sizing of the core yarn Starchstandard Specific Specific (B12 from the (TD52M from (TD52M from companyNAG) the company the company Vetrotex) Vetrotex) Titer of the composite108 tex 110 tex — yarn after the 1^(st) coating Titer of the composite135 tex 140 tex 166 tex yarn after the 2^(nd) coating Breaking strengthof the 50N 54N 42N final composite yarn (measured with a, as one exampleof the type of machine that can be used for this assessment, at atensile speed of 50 mm/min),

TABLE 6 Composite yarn Composite yarn Control A according to B accordingto composite yarn the embodiment the embodiment C Textile 18 × 14 weave18 × 14 weave 18 × 14 weave Weight of the textile 450 450 520 per m² ing Thickness in mm of 0.67 0.67 0.75 the textile Opening factor of the5.5% 5.5% 5.0% textile in % (measured with a spectrophotometer at 650nm) Fire test class M1 M1 M1 according to standard NF P-92507 Visualevaluation of Weak Weak Strong the smoke during combustion UV stabilityaccording 7/8 7/8 7/8 to standard ISO 105B02 Mechanical strength Class 3Class 3 Class 3 tests according to EN (>10 000 (>10 000 (>10 000 13561cycles) cycles) cycles)

As seen in Tables 5 and 6, the properties of yarns A and B were revealedto be greater than those of the control yarn, irrespective of the coreyarn (standard for yarn A or specific for yarn B). Tables 7 and 8 belowreveal the differences in composition between the control yarn C andyarn B according to one embodiment made with the same core yarn. Theseresults also apply to yarn A, which uses the same plastisols as yarn Band which is made with a textile glass yarn having an identical titer tothat of the textile glass yarn used for making yarns B and C.

TABLE 7 Composite yarn according to the Control Component embodimentcomposite yarn Core yarn made of textile 50.4% 42.3% glass yarnPlasticizer 14.0% 14.8% Flame retardant(s)  1.9%  7.5% Inorganicreinforcing filler  4.5% — PVC 26.8% 32.5% Opacifier (zinc sulfide) 1.0%  1.0% Various additives  1.5%  1.9% TOTAL (weight %)  100%  100%

It was thus seen that yarn B according to one embodiment includes anamount of fire-retardant filler equal to about 25% (i.e., the ratio of1.9% to 7.5%) by weight of the amount of fire-retardant filler of thecontrol yarn C, for the same fire resistance class. Thus, the amount offire-retardant filler was able to be reduced by about 75% to obtain alevel of flame retardancy similar to that of the control composite yarn.

This leads to a significant drop in production costs. Thus, for thecomposite yarn according to the embodiment comprising a textile glassyarn as core yarn and a PVC plastisol, this results in a significantreduction in the costs of the PVC plastisol, of the order of 25% to 35%,to obtain a fire compliance result identical to that obtained accordingto the prior art, for example the class M1 according to the presentexample.

TABLE 8 Weight ratio of Composite Control composite components yarn Byarn C % sheath (matrix + layer) 50.5% 58.8% Plasticizer/core yarns14.3% 14.7% Plasticizer/PVC 52.4% 45.4% Flame retardant/organic 4.5%15.2% materials Mineral materials/organic 17.3% 17.2% materials Flameretardant/plasticizer 13.5% 50.5%

It was thus seen that yarn B according to the embodiment has a similarmineral materials/organic materials ratio (58.8% for the control yarn C;50.5% maximum for yarn B), whereas the flame retardant/organic materialsratio is greatly reduced (15.2% for yarn C; 4.5% for yarn B). However,yarn B makes it possible to obtain the same level of fire performance.

In addition, the use of a reinforcing filler makes it possible to obtainhigher mechanical properties (increase in the breaking strength of theyarn by 18.5%: 54 N for yarn B and 42 N for yarn C; see Table 5),whereas the overall level of plasticization of the two yarns is similar(14.7% for yarn C; 14.3% for yarn B; see Table 8), which ensuresequivalent flexibility for the 2 yarns.

In sum, a composite yarn is disclosed wherein the use of particles in amatrix enables the material, by virtue of the particles that areincorporated therein, to be present in the inter-filament interstices ofthe core yarn. The particles interact both with the core yarn filamentsand with the matrix polymer to provide one or more of the benefitsdescribed above, based on the disclosed parameters and the desiredapplication.

Example 2

1. Composite Yarns

One composite yarn according to one embodiment (D) was manufactured,from PVC plastisol, by two successive coatings of the same PVC plastisolcoating containing flame-retardant particles and silanized glassmicrobeads as reinforcing filler on a core yarn. The core yarn is thestandard textile glass yarn composed with a low torsion (28 rounds permeter) of Example 1 and a title of 68 tex. Two types of silanized glassbeads were used. The silanized glass beads Microperl® had a hardness of5.5 Mohs. They were spherical and had an average diameter of 20 μm, witha d_(v50) of 30 μm, a d_(v10) of 15 μm and a d_(v90) of 80 μm, asmeasured for example by laser particle size measurement using a MalvernMasterizer 2000 Instrument machine. The silanized glass beads Omicron®had a hardness of 5.5 Mohs. They were spherical and had an averagediameter of 5 μm, with a d_(v50) of 7 μm, a d_(v10) of 2 μm and ad_(v90) of 15 μm, as measured for example by laser particle sizemeasurement using a Malvern Masterizer 2000 Instrument machine.

One control composite yarn (E) was also used, which is a commercialproduct of the Applicant, made by two successive coatings of the samePVC plastisol on a core yarn. The core yarn is the specific textileglass yarn with a high torsion (52 rounds per meter) of Example 1 and atitle of 68 tex. This commercial product has the best fire performanceamong the commercial products sold by the Applicant, thus meeting boththe fire performance criteria “M1” of standard NF 92-503 and the fireperformance criteria “B1” of standard DIN 4102-1.

The compositions of the plastisol used are given in Tables 9 and 10below.

TABLE 9 Composite yarn according to the embodiment D Sheath sheathcomposition in sheath composition PHR (per composition in wt % of theComponent hundred (PVC) in wt % of composite function Component resin)the sheath yarn Plasticizer 1 Benzoate dioctyl 37.0 20.2% 10.%terephtalate Plasticizer 2 PLF 290 from the 5.0 2.7% 1.4% company ThorHeat Liquid stabilizer of 3.0 1.6% 0.8% stabilizer Ba/Zn type Flame-Zinc 5.0 2.7% 1.4% retardant 1 hydroxystannate Flame- Alumina hydrate10.0 5.5% 2.8% retardant 2 Flame- Phosphorous 5.0 2.7% 1.4% retardant 3ceramic powders Inorganic Silanized glass 12.8 7.0% 3.6% filler 1 beads(Microperl ® 050-20 from the company Sovitec) Inorganic Silanized glass3.2 1.7% 0.9% filler 2 beads (Omicron ® 110-P8 from the company Sovitec)Opacifier Zinc sulfide (ZnS) in 1.1 0.6% 0.3% a plasticizer of DIDPterephthalate type in a 70/30 ratio (weight/weight) PVC resin PB1302from the 68 37.2% 19.0% company Kem-one PVC resin EXT from the 32 17.5%8.9% company Vinnolit Fumed silica Wacker ® AK 50 0.8 0.4% 0.2% siliconeoil from the company Wacker Chemie Total I 182.7 100.0% 50.7%

The RV-type Brookfield viscosity of this plastisol was: 900 mPa·s(measured with a No. 3 spindle at 23° C.). The temperature of the yarnat the outlet of the coating line was: 155° C.

The title of the composite yarn D according to the embodiment thusobtained was 139 tex.

TABLE 10 Control composite yarn E Sheath Sheat composition in sheathcomposition PHR (per composition in wt % of the Component hundred (PVC)in wt % of composite function Component resin) the sheath yarnPlasticizer Diisodecyl phthalate 45.5 25.9% 15.2% (DIDP) Heat Liquidstabilizer of 5.0  2.8% 1.7% stabilizer Ba/Zn type Flame- Base on anti-23.0 13.0% 7.8% retardant monytrioxide and zinc hydrostannate OpacifierZinc sulfide (ZnS) in 1.1  0.6% 0.4% a plasticizer (terephthalate type)in a 70/30 ratio (weight/weight) PVC resin PB1302 from the 80 45.6%26.8% company Kem-one PVC resin EXT from the 20 11.4% 6.7% companyVinnolit Lubricant Wacker ® AK 50 0.9  0.5% 0.3% silicone oil from thecompany Wacker Chemie Total 175.5  100% 58.8%

The RV-type Brookfield viscosity of this plastisol was: 1300 mPa·s(measured with a No. 3 spindle at 23° C.). The temperature of the yarnat the outlet of the coating line was: 135° C.

The title of the control composite yarn E thus obtained was 165 tex.

2. Results

The two composite yarns and the corresponding textiles obtained by thesame operation for the weaving of these composite yarns had thecharacteristics given, respectively in Tables 11, 12 and 13 below.

TABLE 11 Control Composite yarn composite yarn D according to E theembodiment Textile 18 × 10 weave 21 × 11 weave Weight of the textile 462455 per m² in g Thickness in mm of 0.57 0.59 the textile Opening factorof the 1.2% 1.3% textile in % (measured with a spectrophotometer at 650nm) Titer of the composite 165 139 yarn in tex Breaking strength of 38N42N the final composite yarn (measured with a, as one example of thetype of machine that can be used for this assessment, at a tensile speedof 50 mm/min),

Composite yarn D according to the embodiment gave textile surfaceshaving substantially similar weight, thickness and opening factors tothat of the textile surface obtained by control composite yarn E, themechanical properties of the two composite yarns are quite similar.

TABLE 12 Control Composite yarn composite yarn D according to E theembodiment % sheath (matrix +   59%   51% layer) % flame  7.8%  5.6%retardant/composite yarn % plasticizer/PVC 45.5%   42% % 15.2% 11.4%plasticizer/composite yarn % flame 15.4% 14.0% retardant/organicmaterials % mineral 15.9% 26.1% materials/organic materials on sheath %flame 50.5% 47.6% retardant/plasticizer

As seen in Tables 11 and 12, in comparison with the control yarn E,composite yarn D according to the embodiment has a slightly lower flameretardant/organic materials ratio (15.4% for control yarn E; 14% forcomposite yarn D), and a slightly lower flame retardant/plasticizerratio (50.5% for control yarn E; 47.6% for composite yarn D).

TABLE 13 Control Composite yarn composite yarn D according to E theembodiment FIGRA_(0.2) in W/s 260 90 THP₆₀₀ in MJ 0.80 0.20 Fire testclass Cs3d0 Bs3d0 according to standard EN 13-501-1

The FIGRA parameter measures the speed of the energetic productionduring the combustion. FIGRA_(0.2) parameter provides the speed level toreach 0.2 MJ. The FIGRA_(0.2) value for Euroclass “B” is less or equalthan 120 W/s.

The THP parameter measures the total energetic production during thecombustion. The THP₆₀₀ parameter provides the energetic production levelreached at 600 s. The THP₆₀₀ value for Euroclass “B” is less or equalthan 7.5 MJ, whereas the THP₆₀₀ for Euroclass “C” is less or equal than15.MJ.

The FIGRA_(0.2) value obtained with the textile made from composite yarnD according to the embodiment reflects, compared to the textile madefrom control yarn E, a very sharp decrease in energy production duringcombustion (90 W/s against 260 W/s) although they have very similarphysical characteristics. This level of performance (FIGRA_(0.2)<100W/s) cannot normally be achieved by glass-fiber-based textiles coatedwith plasticized PVC.

Therefore, only composite yarn D makes it possible to meet therequirements of Euroclass “B” of standard EN 13-501-1, the control yarnmeeting only the requirement of Euroclass “C” of standard EN 13-501-1.However, the textile surface obtained by composite yarn D according tothe embodiment has a greatly improved fire performance although it has alower flame retardant content than the textile surface obtained bycontrol yarn E (5.6% against 7.8%) and a slightly lower flameretardant/plasticizer ratio (47.6% against 50.5%).

To the knowledge of the Applicant, this is the first time that acomposite yarn obtained by coating a flame retardant plastisol on aglass textile yarn can meet the requirements of Euroclass “B” ofstandard EN 13-501-1.

1-25. (canceled)
 26. A process for manufacturing a composite yarncomprising a continuous multifilament core yarn incorporated in amatrix, said process comprising at least one step of depositing, bycoating or extrusion, a matrix comprising a polymer material and areinforcing filler formed from functionalized particles, onto a coreyarn.
 27. The process according to claim 26, wherein the reinforcingfiller is dispersed throughout the polymer before depositing.
 28. Theprocess according to claim 26, wherein some of the filler is present inthe inter-filament interstices of the core yarn.
 29. The processaccording to claim 26, wherein the depositing step is performed bycoating with a plastisol on the filaments of the core yarn.
 30. Theprocess according to claim 26, further comprising at least one coatingstep, on the composite yarn manufactured at the depositing step bycoating or extrusion, of at least one layer of polymer material in whichis dispersed at least one reinforcing filler, onto the composite yarnobtained in the depositing step.
 31. The process according to claim 30,wherein the coating step is performed by coating with a plastisol or byextrusion of a compound.
 32. The process according to claim 30, whereinthe coating step is performed by extrusion-coating of a composite yarnobtained in the depositing step with a compound in which is dispersed atleast one reinforcing filler.
 33. The process according to claim 30,wherein the layer of polymer material further comprises at least onefire-retardant filler.
 34. A composite yarn obtained by the processaccording to claim 26, comprising a continuous multifilament core yarnincorporated in a matrix, wherein the matrix comprises at least onepolymer material and at least one reinforcing filler, the reinforcingfiller being formed from functionalized particles.
 35. The compositeyarn according to claim 34, wherein the composite yarn has a titer of135-140.
 36. The composite yarn according to claim 34, wherein thecontinuous multifilament core yarn has a torsion within the range offrom 20 to 40 rounds per meter.
 37. The composite yarn according toclaim 34, wherein the average diameter of each of the filaments of thecore yarn is within the range from 3.5 μm to 13 μm.
 38. The compositeyarn according to claim 34, wherein the ratio between the median size(d_(v50)) of the reinforcing particles and the diameter of each of thefilaments of the core yarn is in the range from 0.15:1 to 12:1.
 39. Thecomposite yarn according to claim 34, wherein the weight percentage ofreinforcing filler present in the composite yarn is within the range of0.5 to 30%.
 40. The composite yarn according to claim 34, wherein theamount of fire-retardant filler in the composite yarn is more than 1.5%and less than 7.5% by weight.
 41. The composite yarn according to claim34, wherein the composite yarn comprises a continuous multi-filamentcore yarn and a matrix, the matrix comprising: (i) at least one polymermaterial, the polymer being chosen from the group consisting of PVCs,polyacrylates, polyolefins, polyesters, polyvinyls, polystyrenes,polyurethanes, EVA polymers and polyamides, and (ii) at least onereinforcing filler, the reinforcing filler being constituted byparticles dispersed in the polymer material of the matrix and present inthe inter-filament interstices of the core yarn, said particles beingfunctionalized, the composite yarn further comprising a flame-retardantfiller in an amount of approximately 0.5 to 5% by weight.
 42. Thecomposite yarn according to claim 34, wherein the composite yarncomprises a continuous multi-filament core yarn and a matrix, the matrixcomprising: (i) at least one polymer material, the polymer being chosenfrom the group consisting of PVCs, polyacrylates, polyolefins,polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers andpolyamides, and (ii) at least one reinforcing filler, the reinforcingfiller being constituted by particles dispersed in the polymer materialof the matrix and present in the inter-filament interstices of the coreyarn, said particles being functionalized, the composite yarn furthercomprising a flame-retardant filler in an amount of approximately 5 to15% by weight.
 43. The composite yarn according to claim 34, wherein theMohs hardness of the particles constituting the reinforcing filler is inthe range from 1 to 5.5.
 44. A textile comprising at least one compositeyarn according to claim
 34. 45. The textile according to claim 44,wherein the textile is selected from sunblinds, sun-blocking textiles,sun-screening textiles, sun-shielding textiles, and combinationsthereof.